US3193569A - Hydroxy, halo and sulfato c2-4 carboxylic acid diesters of 3, 5 di-(hydroxymethyl) 4-loweralkyl aniline - Google Patents
Hydroxy, halo and sulfato c2-4 carboxylic acid diesters of 3, 5 di-(hydroxymethyl) 4-loweralkyl aniline Download PDFInfo
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- US3193569A US3193569A US248251A US24825162A US3193569A US 3193569 A US3193569 A US 3193569A US 248251 A US248251 A US 248251A US 24825162 A US24825162 A US 24825162A US 3193569 A US3193569 A US 3193569A
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- sulfato
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- carboxylic acid
- loweralkyl
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- -1 carboxylic acid diesters Chemical class 0.000 title description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title description 4
- 125000001475 halogen functional group Chemical group 0.000 title 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000005181 nitrobenzenes Chemical class 0.000 description 3
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 3
- 229910003446 platinum oxide Inorganic materials 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- FIJPWGLOBMXXSF-UHFFFAOYSA-M potassium;2-hydroxyacetate Chemical compound [K+].OCC([O-])=O FIJPWGLOBMXXSF-UHFFFAOYSA-M 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 238000006149 azo coupling reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LFEINUNSYODISY-UHFFFAOYSA-N (ent-5alpha,6beta)-15,16-Epoxy-3,13(16),14-clerodatrien-18,6-olide Natural products CC1CC(C23C)OC(=O)C3=CCCC2C1(C)CCC=1C=COC=1 LFEINUNSYODISY-UHFFFAOYSA-N 0.000 description 1
- TVFFHYVZRRVAGJ-UHFFFAOYSA-N 1,3-bis(chloromethyl)-2-methyl-5-nitrobenzene Chemical compound CC1=C(CCl)C=C([N+]([O-])=O)C=C1CCl TVFFHYVZRRVAGJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JFGQHAHJWJBOPD-UHFFFAOYSA-N 3-hydroxy-n-phenylnaphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=CC=C1 JFGQHAHJWJBOPD-UHFFFAOYSA-N 0.000 description 1
- CWJQQASJVVAXKL-UHFFFAOYSA-N 4-(3-Methyl-5-oxo-4,5-dihydro-1H-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1CC(C)=NN1C1=CC=C(S(O)(=O)=O)C=C1 CWJQQASJVVAXKL-UHFFFAOYSA-N 0.000 description 1
- QRYRORQUOLYVBU-VBKZILBWSA-N Carnosic acid Natural products CC([C@@H]1CC2)(C)CCC[C@]1(C(O)=O)C1=C2C=C(C(C)C)C(O)=C1O QRYRORQUOLYVBU-VBKZILBWSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical class [H]C([H])(Cl)* 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical class C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- HKYGSMOFSFOEIP-UHFFFAOYSA-N dichloro(dichloromethoxy)methane Chemical compound ClC(Cl)OC(Cl)Cl HKYGSMOFSFOEIP-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004674 formic acids Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
- C07C205/42—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
- C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
- C09B62/82—Azo dyes
Definitions
- R is selected from the group consisting of H and lower alkyl, n has a value of l to 3, Y is selected from the group consisting of NH and N0 and X is selected from the group consisting of OH and ester-forming anions of a strong acid having a dissociation constant greater than 2.0 10-
- the invention also includes processes for producing compounds of the above formula comprising reacting by heating one mole of a benzene compound of the formula I R1- s R Xl-CHgCl wherein R Z and R are selected from the group consisting of H, halogen, lower alkyl and lower alkoxy, and R is selected from the group consisting of H, halogen, lower alkyl, lower alkoxy, and CH Cl with an amount of a compound of the formula M-OOC(CHR) OH, wherein M is alkali metal, R is selected from the group consisting of H and lower alkyl, and n has a value of l to 3, about molecularly equivalent to the number of
- R, R R Z, R and R may be H or lower alkyl such as methyl to butyl or isomers thereof.
- R R Z, R and R may be any halogen including F or I but preferably C1 or Br, or lower alkoXy ice Such as methoxy to butoxy or isomers thereof.
- R may also be CH Cl and R may also be n has a value of 1 to 3.
- X in the above formula represents OH or an esterforming anion as defined above, the preferred anions being Cl and 080 1-1.
- X may represent the anion of any other strong acid such as the anions of hydrobromic, hydrofluoric, ioclic, phosphoric, phosphouic, phosphinic, organic sulfonic (sulfonyloxy), trichloroacetic, dichloroacetic, chloracetic, formic acids and the like.
- the fundamental reaction for producing the compounds of this invention requires the use as precursor of a nitrobenzene containing at least one meta-substituted chloromethyl group.
- a nitrobenzene containing at least one meta-substituted chloromethyl group examples include US. 2,768,217.
- These and other suitable precursors for use in the present invention may generally be prepared by reaction of an appropriately substituted or unsubstituted nitrobenzene compound with one or two moles of a chloromethylating agent such as bis-chloromethyl ether in the presence of sulfuric acid.
- chloromethylation of the nitrobenzene compound may be carried out by reaction with formaldehyde, zinc chloride and HCl.
- the hydroxylic carboxylic acid salt of the formula MOOC(CHR) OI-l, wherein M is any alkali metal but preferably potassium or sodium, are known compounds and/or are prepared in known manner.
- the alkali metal salt of gamma-hydroxybutyric acid is prepared by treatment of gamma-butyrolactone, or lower alkyl substituted derivatives thereoiQwith an aqueous alkali metal hydroxide solution.
- the alkali metal salt of ,B-hydroxypropionic acid is prepared by like treatment of e-pro iolactone or its lower alkyl substituted derivatives.
- the alkali metal salts of glycolic acid or lower alkyl substituted derivatives thereof may also be employed for reaction with the chloromethylated nitrobenzene precursor.
- the reaction between the chloromethylated nitrobenzene precursor and the hydroxylated carboxylic acid salt is preferably-carried out in a polar organic solvent for the reactants. While methanol is preferred, other suitable solvents may be employed as for example, ethanol, butanol, Cellosolves (lower alkyl and benzyl ethers of ethylene glycol), Carbitols (lower alkyl ethers of diethylene glycol), dioxane, acetone, methyl ethyl ketone, and the like. Reaction takes place at any temperature from room temperature up to the boiling point of the medium although elevated temperatures, for example at least 50 C., are preferred to accelerate the reaction. The alkali metal chloride by-product is precipitated during the reaction and readily removed as by filtration after which the desired product may be recovered or isolated if desired by evaporating the solvent from the medium.
- a polar organic solvent for the reactants. While methanol is preferred, other suitable solvents may be employed as for example
- the substituted nitrobenzene product of the process described in the preceding paragraph may if desired then be subjected to the action of a reducing agent to convert the nitro group to amino in any manner well known in the art. In such instances, it is preferred for economic reasons to dispense with a separation step and to instead treat the substituted nitrobenzene compound with the reducing agent in its alcoholic or other polar organic solvent solution.
- This may for example be conveniently carried out by subjecting the filtrate containing the substituted nitrobenzene compound, after removal of the by-product alkali metal chloride, to reduction by the well known catalytic hydrogenation process involving injection of molecular hydrogen, preferably under pressure, in the presence of a suitable catalyst such asRaney nickel, platinum, palladium, and/ or their oxides, or combinations thereof, preferably on a carrier such as charcoal or other known equivalents thereof.
- a suitable catalyst such asRaney nickel, platinum, palladium, and/ or their oxides, or combinations thereof
- products wherein Y is NH and X is OH may be diazotized and coupled with any known azo coupling component. Esterification of the resulting azo dyestuif to replace the terminal OH group by an ester group yields a dyestuff reactive with textile fibers such as cotton under alkaline conditions with liberation of HX.
- Compounds wherein Y is NH and X is an ester radical as defined above may be similarly diazotized and coupled With an azo coupling component to yield a fiber-reactive azo dyestufi.
- Example 1 A solution is prepared with 1900 parts by volume ethanol and 93.6 parts by weight 2,6-bis-chloromethyll-nitrotoluene. After dissolving is completed at the boil, 128 parts by weight of B-hydroxypropionic acid potassium salt are added and rinsed into the charge by means of 100 parts by volume ethanol. chloride has separated, and is removed by filtration. All the alcohol is then evaporated on a steam bath leaving the reaction product of the structure:
- Example 2 A pressure shaker is charged with 200 parts by volume ethanol, 50 parts by Weight of the nitro compound of Example 1, and 0.5 part by weight platinum oxide catalyst (Adams catalyst). Hydrogen is charged to'a pressure of 58 lbs. Within minutes the hydrogen pressure drops to lbs. Again hydrogen is added to a pressure of 58 lbs. The pressure drops to lbs. within 35 minutes and remain constant for 1 hour indicating the completeness of the reduction. The catalyst is filtered off and ethanol is removed by evaporation on a steam bath.
- the reduction product' has the structure:
- Example 3 A charge of 250 parts by volume ethanol, 11.7 parts by weight 2,6-bis(chl onomethyl)-4-nitrotoluene and 11.8 parts by weight gamma-hydroxybutyric acid potassium salt is heated to reflux under agitation. Potassium chloride begins to precipitate from the solution initially formed. After stirring at reflux for 2 hours the solution is filtered hot to remove the potassium chloride. The clear filtrate contains the compound of the structure:
- platinum oxide catalyst Adams catalyst
- Example 5 The entire product from Example 4 is introduced into parts by volume conc. hydrochloric acid. The charge is then stirred at 72-75 C. for 2 /2 hours, by which time the reaction product has precipitated and is filtered off at room'temperature and sucked down sharply. It has the structure:
- Example 6 A charge of 250 parts by volume methanol, 11.7 parts by weight 2,6-bis(chloromethyl)-4-nitrotoluene and 22.9
- glycolic acid potassium salt is refluxed for 1 15 hours.
- Example 8 CHr- NHz 4.5 parts by weight of 2,6-bis(fl-hydroxypropionatomethyl)-4-amino-toluene, prepared as described in Example 2, are introduced at below 20 C. into 10 parts by volume monohydrate (100% H 80 The charge is agitated at room temperature for 14 hours and drowned in ice to produce the above di-sulfato product.
- n is an integer of 1 to 3
- X is selected from the group consisting of OH, halogen and sulfato.
- a compound of the formula CH3 3.
Description
United States Patent HYDRQXY, HALG AND SULFATO C CARBGX- YLlC ACID DTEETEREl @lt 3,5 Dl-(HYDROXY- METHYL) 4-LGWERALKYL ANTLHNE Wilhelm Schmidt-Nickels, Little York, N..l., assignor to General Aniline 3; Film (Importation, New York, N.Y., a corporation of Delaware No Drawing. Filed Dec. 31, 1962, Ser. No. 248,251
6 Claims. (Cl. 266-458) wherein R Z and R are selected from the group consisting of H, halogen, lower alkyl and lower alkoxy, R is selected from the group consisting of H, halogen, lower alkyl, lower alkoxy, and
R is selected from the group consisting of H and lower alkyl, n has a value of l to 3, Y is selected from the group consisting of NH and N0 and X is selected from the group consisting of OH and ester-forming anions of a strong acid having a dissociation constant greater than 2.0 10- The invention also includes processes for producing compounds of the above formula comprising reacting by heating one mole of a benzene compound of the formula I R1- s R Xl-CHgCl wherein R Z and R are selected from the group consisting of H, halogen, lower alkyl and lower alkoxy, and R is selected from the group consisting of H, halogen, lower alkyl, lower alkoxy, and CH Cl with an amount of a compound of the formula M-OOC(CHR) OH, wherein M is alkali metal, R is selected from the group consisting of H and lower alkyl, and n has a value of l to 3, about molecularly equivalent to the number of --CH Cl groups in said benzene compound. To produce compounds wherein Y is NH the foregoing process is followed by the step of subjecting the product thereof tothe action of a reducing agent. To produce compounds of the invention wherein X is other than OH, namely an ester radical, the product of the foregoing process is esterified by reaction with a strong acid having a dissociation constant greater than 2.0
In the above formula, R, R R Z, R and R may be H or lower alkyl such as methyl to butyl or isomers thereof. R R Z, R and R may be any halogen including F or I but preferably C1 or Br, or lower alkoXy ice Such as methoxy to butoxy or isomers thereof. R may also be CH Cl and R may also be n has a value of 1 to 3.
X in the above formula represents OH or an esterforming anion as defined above, the preferred anions being Cl and 080 1-1. Alternatively, X may represent the anion of any other strong acid such as the anions of hydrobromic, hydrofluoric, ioclic, phosphoric, phosphouic, phosphinic, organic sulfonic (sulfonyloxy), trichloroacetic, dichloroacetic, chloracetic, formic acids and the like.
The fundamental reaction for producing the compounds of this invention requires the use as precursor of a nitrobenzene containing at least one meta-substituted chloromethyl group. Examples of such precursors are disclosed in the prior art including US. 2,768,217. These and other suitable precursors for use in the present invention may generally be prepared by reaction of an appropriately substituted or unsubstituted nitrobenzene compound with one or two moles of a chloromethylating agent such as bis-chloromethyl ether in the presence of sulfuric acid. Alternatively, chloromethylation of the nitrobenzene compound may be carried out by reaction with formaldehyde, zinc chloride and HCl.
The hydroxylic carboxylic acid salt of the formula MOOC(CHR) OI-l, wherein M is any alkali metal but preferably potassium or sodium, are known compounds and/or are prepared in known manner. Thus, the alkali metal salt of gamma-hydroxybutyric acid is prepared by treatment of gamma-butyrolactone, or lower alkyl substituted derivatives thereoiQwith an aqueous alkali metal hydroxide solution. Similarly, the alkali metal salt of ,B-hydroxypropionic acid is prepared by like treatment of e-pro iolactone or its lower alkyl substituted derivatives. The alkali metal salts of glycolic acid or lower alkyl substituted derivatives thereof may also be employed for reaction with the chloromethylated nitrobenzene precursor.
The reaction between the chloromethylated nitrobenzene precursor and the hydroxylated carboxylic acid salt is preferably-carried out in a polar organic solvent for the reactants. While methanol is preferred, other suitable solvents may be employed as for example, ethanol, butanol, Cellosolves (lower alkyl and benzyl ethers of ethylene glycol), Carbitols (lower alkyl ethers of diethylene glycol), dioxane, acetone, methyl ethyl ketone, and the like. Reaction takes place at any temperature from room temperature up to the boiling point of the medium although elevated temperatures, for example at least 50 C., are preferred to accelerate the reaction. The alkali metal chloride by-product is precipitated during the reaction and readily removed as by filtration after which the desired product may be recovered or isolated if desired by evaporating the solvent from the medium.
The substituted nitrobenzene product of the process described in the preceding paragraph may if desired then be subjected to the action of a reducing agent to convert the nitro group to amino in any manner well known in the art. In such instances, it is preferred for economic reasons to dispense with a separation step and to instead treat the substituted nitrobenzene compound with the reducing agent in its alcoholic or other polar organic solvent solution. This may for example be conveniently carried out by subjecting the filtrate containing the substituted nitrobenzene compound, after removal of the by-product alkali metal chloride, to reduction by the well known catalytic hydrogenation process involving injection of molecular hydrogen, preferably under pressure, in the presence of a suitable catalyst such asRaney nickel, platinum, palladium, and/ or their oxides, or combinations thereof, preferably on a carrier such as charcoal or other known equivalents thereof.
Other methods of reduction may be employed including the use of the well known-reduction system containing a strong acid HX having a dissociationconstant greater than 2.0 10 For example, treatment with concentrated HCl or thionyl chloride yields the correspondingcompound wherein X is Cl. such as sulfuric acid or pyridine-S0 complex yields the correspondingcompound wherein X is OSO H. Alternatively, other esterifying acids of the type described above may be employed.
The products of this invention are surprisingly effective in the production of dyestuffs and other ohromophoric compounds reactive with textile fibers, as described and claimed in my co-pendingapplication Serial No. 248,243 filed on even date herewith. Thus, products wherein Y is NH and X is OH, as in Example 2 below, may be diazotized and coupled with any known azo coupling component. Esterification of the resulting azo dyestuif to replace the terminal OH group by an ester group yields a dyestuff reactive with textile fibers such as cotton under alkaline conditions with liberation of HX. Compounds wherein Y is NH and X is an ester radical as defined above may be similarly diazotized and coupled With an azo coupling component to yield a fiber-reactive azo dyestufi.
The following examples are only illustrative of the present invention and are not to be regarded as limitative. All parts and proportions referred to herein and in the appended claims are by weight unless otherwise indicated.
Example 1 A solution is prepared with 1900 parts by volume ethanol and 93.6 parts by weight 2,6-bis-chloromethyll-nitrotoluene. After dissolving is completed at the boil, 128 parts by weight of B-hydroxypropionic acid potassium salt are added and rinsed into the charge by means of 100 parts by volume ethanol. chloride has separated, and is removed by filtration. All the alcohol is then evaporated on a steam bath leaving the reaction product of the structure:
HO-CH2CHFC O O-CH2 Example 2 A pressure shaker is charged with 200 parts by volume ethanol, 50 parts by Weight of the nitro compound of Example 1, and 0.5 part by weight platinum oxide catalyst (Adams catalyst). Hydrogen is charged to'a pressure of 58 lbs. Within minutes the hydrogen pressure drops to lbs. Again hydrogen is added to a pressure of 58 lbs. The pressure drops to lbs. within 35 minutes and remain constant for 1 hour indicating the completeness of the reduction. The catalyst is filtered off and ethanol is removed by evaporation on a steam bath. The reduction product'has the structure:
n0-o1n-om-c 0 0,-0112 After refluxing overnight potassium Reaction with a sulfating agent a The above product is diazotized, coupled with 1-(4- sulfophenyl)-3-methyl-5-pyrazolone, and esterified with concentrated HCl to produce an azo dyestuif containing two fiber-reactive ClCH CH 'COO-CH groups and yielding on cotton by the alkaline pad-cure method a bright yellow dyeing of good fastness properties. Similar results are obtained if the above product is esterified with concentrated HCl prior to diazotization and coupling.
Example 3 A charge of 250 parts by volume ethanol, 11.7 parts by weight 2,6-bis(chl onomethyl)-4-nitrotoluene and 11.8 parts by weight gamma-hydroxybutyric acid potassium salt is heated to reflux under agitation. Potassium chloride begins to precipitate from the solution initially formed. After stirring at reflux for 2 hours the solution is filtered hot to remove the potassium chloride. The clear filtrate contains the compound of the structure:
Example 4 The filtrate from Example 3 is charged directly into a pressure shaker. After addition of 0.3 g. platinum oxide catalyst (Adams catalyst), hydrogen is charged to a pressure of 50 lbs. Within 40 minutes the hydrogen pressure falls to 44 lbs. and then remains constant. After removal of the catalyst by filtration the ethanol is evaporated on a steam bath. Weight of remainder=20.3 parts by weight of the reduced product of Example 3.
Example 5 The entire product from Example 4 is introduced into parts by volume conc. hydrochloric acid. The charge is then stirred at 72-75 C. for 2 /2 hours, by which time the reaction product has precipitated and is filtered off at room'temperature and sucked down sharply. It has the structure:
A sample of this product is diazotized and coupled with 1-(4-sulfophenyl)-3-methylpyrazolone-5. The resulting yellow dyestuff is applied to cotton as described in Example 2. The cotton is dyed yellow With similar fastness properties.
Example 6 A charge of 250 parts by volume methanol, 11.7 parts by weight 2,6-bis(chloromethyl)-4-nitrotoluene and 22.9
parts by weight glycolic acid potassium salt is refluxed for 1 15 hours.
After allowing to cool to room temperature the potassium chloride formed in the reaction together with most of the excess glycolic acid potassium salt is re moved by filtration; Then the methanol is evaporated on a steambath. The remainder is dissolved in 200 parts by volume boiling ethanol. On cooling to room temperature some retained glycolic acid potassium salt crystallizes out. Itis filtered ofi. The filtrate contains the reaction product of the structure:
p The filtrate from Example 6 is charged into a pressure shaker. After addition of 0.2 part by weight platinum oxide catalyst (Adams catalyst), hydrogen is charged to a pressure of 45 bs. Within minutes the hydrogen pressure falls to 32 lbs. and then remains at 32 lbs. for minutes. After removal of the catalyst by filtration the ethanol is evaporated on a steam bath. The remaining product has the structure:
The above product, when diazotized, coupled, esterified and applied to cotton as described in Example 2, yields similar results.
Example 8 CHr- NHz 4.5 parts by weight of 2,6-bis(fl-hydroxypropionatomethyl)-4-amino-toluene, prepared as described in Example 2, are introduced at below 20 C. into 10 parts by volume monohydrate (100% H 80 The charge is agitated at room temperature for 14 hours and drowned in ice to produce the above di-sulfato product.
The above product, when diazotized, coupled with Naphthol AS and applied to cotton by the alkaline padcure method (padded on cotton from an alkaline solution, dried, cured, e.g., at 150 C. and washed with detergent to remove unreacted dyestulf) yields red dyeings of good fastness properties.
This invention has been disclosed with respect to certain preferred embodiments and various modifications and variations thereof will become obvious to the person skilled in the art. It is to be understood that such modifications and variations are to be included within the spirit and scope of this invention.
I claim:
1. A compound of the formula wherein Z is lower alkyl,
n is an integer of 1 to 3, and
X is selected from the group consisting of OH, halogen and sulfato.
2. A compound of the formula CH3 3. A compound of the formula HO-CHz-CHrCHz-COO-OHz- CHg-OOO-CHz-C HrCHa-OH 4. A compound of the formula CHz-O O O-CHz-CHa-CHrCl 5. A compound of the formula (ll-CHz-CHg-ClIz-COO-CHF 6. A compound of the formula References Cited by the Examiner UNITED STATES PATENTS 8/54 Salvin et al. 857
OTHER REFERENCES LORRAINE A. WEINBERGER, Acting Primary Examiner.
LEON ZITVER, Examiner.
Claims (1)
1. A COMPOUND OF THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US248251A US3193569A (en) | 1962-12-31 | 1962-12-31 | Hydroxy, halo and sulfato c2-4 carboxylic acid diesters of 3, 5 di-(hydroxymethyl) 4-loweralkyl aniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US248251A US3193569A (en) | 1962-12-31 | 1962-12-31 | Hydroxy, halo and sulfato c2-4 carboxylic acid diesters of 3, 5 di-(hydroxymethyl) 4-loweralkyl aniline |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3193569A true US3193569A (en) | 1965-07-06 |
Family
ID=22938305
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US248251A Expired - Lifetime US3193569A (en) | 1962-12-31 | 1962-12-31 | Hydroxy, halo and sulfato c2-4 carboxylic acid diesters of 3, 5 di-(hydroxymethyl) 4-loweralkyl aniline |
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| Country | Link |
|---|---|
| US (1) | US3193569A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3328454A (en) * | 1963-08-12 | 1967-06-27 | Hooker Chemical Corp | Polyhalobenzyloxyalkanol sulfates |
| US3429687A (en) * | 1963-08-12 | 1969-02-25 | Hooker Chemical Corp | Herbicidal mixture and method of use |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2687941A (en) * | 1954-08-31 | Dyestuffs |
-
1962
- 1962-12-31 US US248251A patent/US3193569A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2687941A (en) * | 1954-08-31 | Dyestuffs |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3328454A (en) * | 1963-08-12 | 1967-06-27 | Hooker Chemical Corp | Polyhalobenzyloxyalkanol sulfates |
| US3429687A (en) * | 1963-08-12 | 1969-02-25 | Hooker Chemical Corp | Herbicidal mixture and method of use |
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